Process for making lube oil basestocks

ABSTRACT

A process for producing lube oil basestocks involving contacting a wax containing feedstock with a stacked bed catalyst system thereby producing a lube oil boiling range basestock.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of U.S. Provisional Patent ApplicationSer. No. 60/518,739 filed Nov. 10, 2003 and Ser. No. 60/608,447 filedSep. 9, 2004.

FIELD OF THE INVENTION

This invention relates to a process for preparing lubricating oilbasestocks from lube oil boiling range feedstreams. More particularly,the present invention is directed at a process wherein a wax containingfeedstock is hydrotreated over a stacked bed catalyst system therebyproducing a lube oil boiling range basestock.

BACKGROUND OF THE INVENTION

It has long been recognized that one of the most valuable productsgenerated through the refining of crude mineral oils is lubricatingoils. It is common practice to recover lubricating oil basestocks bysolvent extracting, with a selective solvent, undesirable componentssuch as sulfur compounds, oxygenated compounds, and aromatics fromstraight distillates. However, with the decline in the availability ofparaffinic base crudes, and a corresponding increase in the proportionof naphthenic and asphaltic base crudes, it is becoming increasinglydifficult to meet the demand for lubricating oil basestocks, or baseoils. For example, American Petroleum Institute (API) requirements forGroup II basestocks include a saturates content of at least 90%, asulfur content of 0.03 wt. % or less and a viscosity index (VI) between80 and 120. Thus, there is a trend in the lube oil market to use GroupII basestocks instead of Group I basestocks in order to meet the demandfor higher quality basestocks that provide for increased fuel economy,reduced emissions, etc.

Conventional techniques for preparing basestocks such as hydrocrackingor solvent extraction require severe operating conditions such as highpressure and temperature or high solvent:oil ratios and high extractiontemperatures to reach these higher basestock qualities. Eitheralternative involves expensive operating conditions and low yields.

Hydrocracking has been combined with hydrotreating as a preliminarystep. However, this combination also results in decreased yields oflubricating oils due to the conversion to distillates that typicallyaccompany the hydrocracking process.

Thus, as the demand for quality lube oil basestock continues toincrease, the search for new and different processes, catalysts, andcatalyst systems that exhibit improved activity, increased yields,selectivity and/or longevity is a continuous, ongoing exercise.Therefore, there is a need in the lube oil market to provide processesthat can produce lube oil basestocks that meet the demand for increasedfuel economy, reduced emissions, etc.

BRIEF DESCRIPTION OF THE FIGURE

The FIGURE is a plot of the relative volume activity of variouscatalysts and catalyst systems versus the days the respective catalystsand catalyst systems were on stream.

SUMMARY OF THE INVENTION

The present invention is directed at a process to prepare lubricatingoil basestocks from lube oil boiling range feedstocks. The processcomprises:

-   -   a) contacting a lube oil boiling range feedstock with a stacked        bed hydrotreating catalyst system in a reaction stage operated        under effective conditions thereby producing a hydrotreated        effluent comprising at least a gaseous product and a        hydrotreated lubricating oil boiling range feedstock; and    -   b) stripping the hydrotreated effluent to remove at least a        portion of the gaseous product from the hydrotreated effluent        thereby producing at least a lubricating oil basestock.

In one embodiment of the instant invention, the stacked bedhydrotreating catalyst system comprises a first and second catalyst, thefirst catalyst comprising a conventional hydrotreating catalyst havingan average pore diameter of greater than about 10 nm and said secondcatalyst comprises a bulk metal hydrotreating catalyst.

DETAILED DESCRIPTION OF THE INVENTION

It should be noted that the terms “feedstock” and “feedstream” as usedherein are synonymous.

The present process involves hydrotreating a lubricating oil feedstockwith a stacked bed hydrotreating catalyst system in a reaction stageoperated under effective hydrotreating conditions to produce ahydrotreated effluent comprising at least a gaseous product and ahydrotreated lubricating oil feedstock. The hydrotreated effluent isstripped to remove at least a portion of the gaseous product from thehydrotreated effluent thereby producing at least a lubricating oilbasestock. Lube oil basestocks having a saturates content of at least90%, a sulfur content of 0.03 wt. % or less, and a viscosity index (VI)between 80 and 120 can readily be produced through the use of theinstant invention.

Lubricating Oil Feedstocks

Feedstocks suitable for use in the present invention are wax-containingfeeds that boil in the lubricating oil range, typically having a 10%distillation point greater than 650° F. (343° C.) and an endpointgreater than 800° F. (426° C.), measured by ASTM D 86 or ASTM 2887.These feedstocks can be derived from mineral sources, synthetic sources,or a mixture of the two. Non-limiting examples of suitable lubricatingoil feedstocks include those derived from sources such as oils derivedfrom solvent refining processes such as raffinates, partially solventdewaxed oils, deasphalted oils, distillates, vacuum gas oils, coker gasoils, slack waxes, foots oils and the like, dewaxed oils, automatictransmission fluid feedstocks, and Fischer-Tropsch waxes. Automatictransmission fluid (“ATF”) feedstocks are lube oil feedstocks having aninitial boiling point between about 200° C. and 275° C., and a 10%distillation point greater than about 300° C. ATF feedstocks aretypically 75-110N feedstocks.

These feedstocks may also have high contents of nitrogen- andsulfur-contaminants. Feeds containing up to 0.2 wt. % of nitrogen, basedon feed and up to 3.0 wt. % of sulfur can be processed in the presentprocess. Feeds having a high wax content typically have high viscosityindexes of up to 200 or more. Sulfur and nitrogen contents may bemeasured by standard ASTM methods D5453 and D4629, respectively.

Hydrotreating

It should be noted that the term “hydrotreating” as used herein refersto processes wherein a hydrogen-containing treat gas is used in thepresence of a suitable catalyst that is primarily active for the removalof heteroatoms, such as sulfur, and nitrogen, and saturation ofaromatics. In the practice of the present invention, the lubricating oilfeedstock is hydrotreated with a stacked bed hydrotreating catalystsystem in a reaction stage operated under effective hydrotreatingconditions to produce a hydrotreated effluent comprising at least agaseous product and a hydrotreated lubricating oil feedstock.

The catalyst system used herein comprises at least a first and secondhydrotreating catalyst. By “stacked bed” it is meant that the firstcatalyst appears in a separate catalyst bed, reactor, or reaction zone,and the second hydrotreating catalyst appears in a separate catalystbed, reactor, or reaction zone downstream, in relation to the flow ofthe lubricating oil feedstock, from the first catalyst.

The first hydrotreating catalyst is a supported catalyst. Suitablehydrotreating catalysts for use as the first catalyst of the presentcatalyst system include any conventional hydrotreating catalyst.Conventional hydrotreating catalyst as used herein is meant to refer tothose which are comprised of at least one Group VIII metal, preferablyFe, Co and Ni, more preferably Co and/or Ni, and most preferably Ni; andat least one Group VI metal, preferably Mo and W, more preferably Mo, ona high surface area support material, preferably alumina. The Group VIIImetal is typically present in an amount ranging from about 2 to 20 wt.%, preferably from about 4 to 12%. The Group VI metal will typically bepresent in an amount ranging from about 5 to 50 wt. %, preferably fromabout 10 to 40 wt. %, and more preferably from about 20 to 30 wt. %. Allmetals weight percents are on support. By “on support” we mean that thepercents are based on the weight of the support. For example, if thesupport were to weigh 100 g. then 20 wt. % Group VIII metal would meanthat 20 g. of Group VIII metal was on the support.

However, not all conventional hydrotreating catalysts fitting theabove-described criteria are suitable for use in the present invention.The inventors hereof have unexpectedly found that the average porediameter of the first catalyst must have a specific size to be suitablefor use herein. Thus, in the practice of the present invention, aconventional catalyst, as described above, but having an average porediameter greater than 10 nm, as measured by water adsorptionporosimetry, must be used as the first catalyst of the present stackedbed catalyst system. It is preferred that the average pore diameter ofthe first catalyst, i.e. the conventional hydrotreating catalyst, of thepresent stacked bed catalyst system be greater than 11 nm, morepreferably greater than 12 nm.

The second hydrotreating catalyst is a bulk metal catalyst. By bulkmetal, it is meant that the catalysts are unsupported wherein the bulkcatalyst particles comprise 30-100 wt. % of at least one Group VIIInon-noble metal and at least one Group VIB metal, based on the totalweight of the bulk catalyst particles, calculated as metal oxides andwherein the bulk catalyst particles have a surface area of at least 10m²/g. It is furthermore preferred that the bulk metal hydrotreatingcatalysts used herein comprise about 50 to about 100 wt. %, and evenmore preferably about 70 to about 100 wt. %, of at least one Group VIIInon-noble metal and at least one Group VIB metal, based on the totalweight of the particles, calculated as metal oxides. The amount of GroupVIB and Group VIII non-noble metals can easily be determined VIBTEM-EDX.

Bulk catalyst compositions comprising one Group VIII non-noble metal andtwo Group VIB metals are preferred. It has been found that in this case,the bulk catalyst particles are sintering-resistant. Thus the activesurface area of the bulk catalyst particles is maintained during use.The molar ratio of Group VIB to Group VIII non-noble metals rangesgenerally from 10:1-1:10 and preferably from 3:1-1:3. In the case of acore-shell structured particle, these ratios of course apply to themetals contained in the shell. If more than one Group VIB metal iscontained in the bulk catalyst particles, the ratio of the differentGroup VIB metals is generally not critical. The same holds when morethan one Group VIII non-noble metal is applied. In the case wheremolybdenum and tungsten are present as Group VIB metals, themolybenum:tungsten ratio preferably lies in the range of 9:1-1:9.Preferably the Group VIII non-noble metal comprises nickel and/orcobalt. It is further preferred that the Group VIB metal comprises acombination of molybdenum and tungsten. Preferably, combinations ofnickel/molybdenum/tungsten and cobalt/molybdenum/tungsten andnickel/cobalt/molybdenum/tungsten are used. These types of precipitatesappear to be sinter-resistant. Thus, the active surface area of theprecipitate is remained during use. The metals are preferably present asoxidic compounds of the corresponding metals, or if the catalystcomposition has been sulfided, sulfidic compounds of the correspondingmetals.

It is also preferred that the bulk metal hydrotreating catalysts usedherein have a surface area of at least 50 m²/g and more preferably of atleast 100 m²/g. It is also desired that the pore size distribution ofthe bulk metal hydrotreating catalysts be approximately the same as theone of conventional hydrotreating catalysts. More in particular, thesebulk metal hydrotreating catalysts have preferably a pore volume of0.05-5 ml/g, more preferably of 0.1-4 ml/g, still more preferably of0.1-3 ml/g and most preferably 0.1-2 ml/g determined by nitrogenadsorption. Preferably, pores smaller than 1 nm are not present.Furthermore these bulk metal hydrotreating catalysts preferably have amedian diameter of at least 50 nm, more preferably at least 100 nm, andpreferably not more than 5000 μm and more preferably not more than 3000μn. Even more preferably, the median particle diameter lies in the rangeof 0.1-50 μm and most preferably in the range of 0.5-50 μm.

The reaction stage containing the stacked bed hydrotreating catalystsystem used in the present invention can be comprised of one or morefixed bed reactors or reaction zones each of which can comprise one ormore catalyst beds of the same or different catalyst. Although othertypes of catalyst beds can be used, fixed beds are preferred. Such othertypes of catalyst beds include fluidized beds, ebullating beds, slurrybeds, and moving beds. Interstage cooling or heating between reactors,reaction zones, or between catalyst beds in the same reactor, can beemployed since some olefin saturation can take place, and olefinsaturation and the desulfurization reaction are generally exothermic. Aportion of the heat generated during hydrotreating can be recovered.Where this heat recovery option is not available, conventional coolingmay be performed through cooling utilities such as cooling water or air,or through use of a hydrogen quench stream. In this manner, optimumreaction temperatures can be more easily maintained.

The catalyst system of the present invention comprises about 5-95 vol. %of the first catalyst with the second catalyst comprising the remainder,preferably about 40-60 vol. %, more preferably about 5 to about 50 vol.%. Thus, if the catalyst system comprises 50 vol. % of the firstcatalyst, the second catalyst will comprise 50 vol. % also.

Effective hydrotreating conditions include temperatures of from 150 to400° C., a hydrogen partial pressure of from 1480 to 20786 kPa (200 to3000 psig), a space velocity of from 0.1 to 10 liquid hourly spacevelocity (LHSV), and a hydrogen to feed ratio of from 89 to 1780 m³/m³(500 to 10000 scf/B).

As stated above, the contacting of the lube oil boiling range feedstockwith the stacked bed hydrotreating catalyst system produces ahydrotreated effluent comprising at least a gaseous product and ahydrotreated lubricating oil feedstock. The hydrotreated effluent isstripped to remove at least a portion of the gaseous product from thehydrotreated effluent thereby producing at least a lubricating oilbasestock The means used herein to strip the hydrotreated effluent isnot critical to the present invention. Thus, any stripping method,process, or means known can be used. Non-limiting examples of suitablestripping methods, means, and processes include flash drums,fractionators, knock-out drums, steam stripping, etc.

The above description is directed to preferred embodiments of thepresent invention. Those skilled in the art will recognize that otherembodiments that are equally effective could be devised for carrying outthe spirit of this invention.

The following examples will illustrate the improved effectiveness of thepresent invention, but is not meant to limit the present invention inany fashion.

EXAMPLES Example 1

A medium vacuum gas oil having the properties outlined in Table 1 wasprocessed in an isothermal pilot plant over three catalysts systems at1200 psig hydrogen partial pressure. The catalyst systems and operatingconditions are given in Table 2. Catalyst B is a conventionalhydrotreating catalyst having about 4.5 wt. % Group VI metal, about 23wt. % Group VIII metal on an alumina support and has an average poresize of 14.0 nm. The bulk metal hydrotreating catalyst was a commercialbulk metal hydrotreating catalyst marketed under the name Nebula byAkzo-Nobel.

In the Examples, all the catalyst systems were lined out at about 50days on stream. A first order kinetic model with an activation energy of31,000 cal/gmol was used to compare volume activities between thecatalysts. TABLE 1 Medium Vacuum Gas Oil Density at 70° C. (g/cc) 0.88Nitrogen (wppm) 700 Sulfur (wt. %) 2.6 GCD 5 WT % Boiling Point (° C.)334 GCD 50 WT % Boiling Point (° C.) 441 GCD 95 WT % Boiling Point (°C.) 531

TABLE 2 50 vol. % Catalyst B 100 vol. % 100 vol. % followed by CatalystSystem Catalyst B Nebula 1 50 vol. % Nebula 1 Average Catalyst 370 380370 Temperature (° C.) Liquid Hourly 2 1 1 Space Velocity (hr⁻¹)Stripped reactor 227 17 34 Effluent Nitrogen Content (wppm) NitrogenRemoval 1 1.18 1.34 Relative Volume Activity

The Nitrogen Removal Relative Volume Activity (“RVA”) for each catalystsystem was calculated by simple first order kinetic modeling. As shownin Table 2, the 50/50 vol. % stacked bed catalyst system, with the largeaverage pore size Catalyst B upstream of the bulk metal catalyst, showedhigher nitrogen removal activity than either of the single catalystsystems demonstrated on their own.

Example 2

The hydrotreating ability of different stacked beds of Catalyst B andNebula were analyzed by hydrotreating different feedstreams over thestacked beds in the in two parallel reactor trains of the sameisothermal pilot plant unit used in Example 1 above. The feedstreamsused were Medium Cycle Oils (“MCO”) from an FCC unit and blends of theMCO with a virgin feedstock were tested in two parallel reactor trains.The feed properties are described in Table 3, below.

In this Example, one reactor train consisted entirely of a conventionalNiMo on Alumina hydrotreating catalyst, Catalyst C, with an average porediameter of 7.5 nm. The other reactor train contained a stacked bedsystem with 75-vol. % of Catalyst C followed by 25-vol. % of Catalyst A,a bulk multimetallic sulfide catalyst having an average pore diameter of5.5 nm.

The separate reactors in both trains were immersed in a fluidizedsandbath for efficient heat transfer. Thus, the temperature of the first75-vol. % of Catalyst C was at the same temperature whether it was intrain 1 or 2. Likewise, the last 25-vol. % of Catalyst C in train 1 wasat the same temperature as the last 25-vol. % of Catalyst A in train 2.Therefore, In Example 2, each of the two reactor trains was divided intotwo separate reactor vessels where the temperature of the first75-volume % containing 75 vol. % of the catalyst loading of that reactorcould be independently controlled from the last 25-volume % of catalyst.

The operating conditions for the two trains were 1350 psig H₂, liquidhourly space velocities (“LHSV”) of 1.4 vol./hr/vol., and 5500-6300SCF/B of hydrogen. The temperature schedule for both trains is describedin Table 4 below. TABLE 3 FEED 50% 67% 100% 100% Normal Normal NormalHeavy FCC MCO FCC MCO FCC MCO FCC MCO API Gravity 18.1 15.0 9.5 7.0Hydrogen, 10.65 10.04 8.77 8.61 wt. % Sulfur, wt. % 3.23 3.53 4.28 4.40Nitrogen, ppm 959 1153 1485 1573 Aromatics- — — 12.0 8.8 Mono, wt. %Aromatics-Di, — — 43.9 41.7 wt. % Aromatics- — — 22.4 30.7 Poly, wt. %Distillation, D2887 GCD 10 498 493 485 493 50 627 625 618 642 90 703 705706 749 95 726 721 724 777

TABLE 4 Days on Oil Feedstock 75%/25% Temperatures, ° F. 4-6  50% FCCMCO 585/650  7-15  67% FCC MCO 585/650 16-30 100% FCC MCO585-610/650-675 31-50 100% Heavy FCC MCO 610-635/675-700

The relative HDN volume activity of the stacked bed Catalyst C/CatalystA compared to Catalyst A is shown in the FIGURE below. Note that for the50%, 67% and 100% FCC MCO feeds the stacked bed system with only25-volume % of catalyst A shows a stable activity advantage of about275%.

As shown in the FIGURE, when the 100% Heavy FCC MCO was used as the feednote the activity advantage for the stacked bed catalyst systemcontaining begins to decrease from about 275% to about 225% and then wassubsequently reduced over about 20 days to slightly less than 150%.

Example 3

In this Example, a stacked bed catalyst system containing 75 vol. % ofCatalyst B and 25 vol. % Nebula, both as described above, was used tohydrotreat a light cycle cat oil feed (“Feed A”) and a heavier mediumcycle cat oil feed (“Feed B”) as described in Table 5 below. Example 2was conducted in the same two reactor train pilot plant unit asdescribed in Example 2 above. The operating conditions for the twotrains were 1200 psig H₂, liquid hourly space velocities of 2vol./hr/vol., and 5000 SCF/B of hydrogen.

The reactor effluents were stripped with nitrogen in an oven at 100° C.to remove substantially all of the gaseous reaction products. Thenitrogen content of the liquid reactor effluent was then analyzed byASTM 4629. The temperature schedules for both trains along with theresults of this example are described in Table 5 below. TABLE 5 FEEDFeed A Feed B API Gravity 0.973 0.9 Sulfur, wt. % 2.6 2.50 Nitrogen, ppm713 742 Distillation, D2887 GCD  5 427 448 50 551 590 95 707 755 EP 764823 Catalyst B Temperature 570 617 Nebula Temperature 645 692 StrippedReactor Effluent 2 7 Nitrogen Content Nitrogen Removal Relative 1.751.75 Volume Activity

As can be seen in Table 5, when a conventional catalyst having anaverage pore diameter of 14 nm was used in the first 75 vol. % of thereactor, the Nitrogen Removal Relative Volume Activity (“RVA”) for thecatalyst system remained constant when the heavier feed was used. Incomparing the results of Example 3 to those obtained in Example 2, onecan see that when a catalyst having a pore volume of 7.5 nm preceded thebulk metal catalyst, the RVA of the catalyst system decreased. However,in Example 3, the heavier feed did not negatively impact the RVA of thecatalyst system.

1. A process to prepare lubricating oil basestocks from a lube oilboiling range feedstock comprising: a) contacting a lube oil boilingrange feedstock with a stacked bed hydrotreating catalyst system in areaction stage operated under effective hydrotreating conditions therebyproducing a hydrotreated effluent comprising at least a gaseous productand a hydrotreated lubricating oil boiling range feedstock; and b)stripping the hydrotreated effluent to remove at least a portion of thegaseous product from the hydrotreated effluent thereby producing atleast a lubricating oil basestock.
 2. The process according to claim 1wherein said lubricating oil feedstock has a 10% distillation pointgreater than 650° F. (343° C.) and an endpoint of greater than 800° F.(426° C.), measured by ASTM D 86 or ASTM 2887, and are derived frommineral sources, synthetic sources, or a mixture of the two.
 3. Theprocess according to claim 2 wherein said lubricating oil feedstock isselected from those derived from sources such as oils derived fromsolvent refining processes such as raffinates, partially solvent dewaxedoils, deasphalted oils, distillates, vacuum gas oils, coker gas oils,slack waxes, foots oils and the like, dewaxed oils, automatictransmission fluid feedstocks, and Fischer-Tropsch waxes.
 4. The processaccording to claim 2 wherein said lubricating oil feedstock contains upto 0.2 wt. % of nitrogen, based on the lubricating oil feedstock, and upto 3.0 wt. % of sulfur, based on the lubricating oil feedstock.
 5. Theprocess according to claim 1 wherein said catalyst system comprises atleast a first and second hydrotreating catalyst.
 6. The processaccording to claim 5 wherein said first hydrotreating catalyst isselected from supported hydrotreating catalysts comprising about 2 to 20wt. % of at least one Group VIII metal, and about 5 to 50 wt. % of atleast one Group VI metal on a high surface area support material havingan average pore diameter of greater than 10 nm.
 7. The process accordingto claim 6 wherein said Group VIII metal is selected from Co Ni, andmixtures thereof, said Group VI metal is selected from Mo, W, andmixtures thereof, and said high surface area support material isselected from silica, alumina, and mixtures thereof.
 8. The processaccording to claim 5 wherein said second catalyst is a bulk metalhydrotreating catalyst comprising about 30 to about 100 wt. % of atleast one Group VIII non-noble metal and at least one Group VIB metal,based on the total weight of the bulk catalyst particles, calculated asmetal oxides and wherein the bulk catalyst particles have a surface areaof at least 10 m²/g.
 9. The process according to claim 8 wherein saidbulk metal hydrotreating catalyst comprises one Group VIII non-noblemetal and two Group VIB metals wherein the molar ratio of Group VIB toGroup VIII non-noble metals ranges from 10:1-1:10.
 10. The processaccording to claim 8 wherein the at least one Group VIII non-noble metaland at least one Group VIB metals are present as oxidic compounds of thecorresponding metals, or if the catalyst composition has been sulfided,sulfidic compounds of the corresponding metals
 11. The process accordingto claim 10 wherein the bulk metal hydrotreating catalysts have asurface area of at least 50 m²/g, a pore size volume of about 0.05 toabout 5 ml/g, and a median diameter of at least 50 nm.
 12. The processaccording to claim 1 wherein said effective hydrotreating conditionsinclude temperatures of from 150 to 400° C., a hydrogen partial pressureof from 1480 to 20786 kPa (200 to 3000 psig), a space velocity of from0.1 to 10 liquid hourly space velocity (LHSV), and a hydrogen to feedratio of from 89 to 1780 m³/m³ (500 to 10000 scf/B).
 13. The processaccording to claim 5 wherein the catalyst system of the presentinvention comprises about 5-95 vol. % of the first hydrotreatingcatalyst with the second hydrotreating catalyst comprising theremainder.
 14. The process according to claim 6 wherein said firsthydrotreating catalyst has an average pore diameter of greater than 11nm.
 15. The process according to claim 6 wherein said firsthydrotreating catalyst has an average pore diameter of greater than 12nm.
 16. The process according to claim 5 wherein the catalyst system ofthe present invention comprises about 40-60 vol. % of the first catalystwith the second hydrotreating catalyst comprising the remainder.
 17. Theprocess according to claim 5 wherein the catalyst system of the presentinvention comprises about 5-50 vol. % of the first catalyst with thesecond hydrotreating catalyst comprising the remainder.
 18. A process toprepare lubricating oil basestocks from a lube oil boiling rangefeedstock comprising: a) contacting a lube oil boiling range feedstockwith a stacked bed hydrotreating catalyst system comprising at least afirst and second hydrotreating catalyst in a reaction stage operatedunder effective hydrotreating conditions thereby producing ahydrotreated effluent comprising at least a gaseous product and ahydrotreated lubricating oil boiling range feedstock; and b) strippingthe hydrotreated effluent to remove at least a portion of the gaseousproduct from the hydrotreated effluent thereby producing at least alubricating oil basestock; wherein said first hydrotreating catalyst isselected from supported hydrotreating catalysts comprising about 2 to 20wt. % of at least one Group VIII metal, and about 5 to 50 wt. % of atleast one Group VI metal on a high surface area support material havingan average pore diameter of greater than 10 nm and said secondhydrotreating catalyst is selected from bulk metal hydrotreatingcatalyst comprising about 30 to about 100 wt. % of at least one GroupVIII non-noble metal and at least one Group VIB metal, based on thetotal weight of the bulk catalyst particles, calculated as metal oxidesand wherein the bulk catalyst particles have a surface area of at least10 m²/g.
 19. The process according to claim 18 wherein said lubricatingoil feedstock has a 10% distillation point greater than 650° F. (343°C.) and an endpoint of greater than 800° F. (426° C.), measured by ASTMD 86 or ASTM 2887, and are derived from mineral sources, syntheticsources, or a mixture of the two.
 20. The process according to claim 19wherein said lubricating oil feedstock is selected from those derivedfrom sources such as oils derived from solvent refining processes suchas raffinates, partially solvent dewaxed oils, deasphalted oils,distillates, vacuum gas oils, coker gas oils, slack waxes, foots oilsand the like, dewaxed oils, automatic transmission fluid feedstocks, andFischer-Tropsch waxes.
 21. The process according to claim 19 whereinsaid lubricating oil feedstock contains up to 0.2 wt. % of nitrogen,based on the lubricating oil feedstock, and up to 3.0 wt. % of sulfur,based on the lubricating oil feedstock.
 22. The process according toclaim 18 wherein said Group VIII metal of said first hydrotreatingcatalyst is selected from Co Ni, and mixtures thereof, said Group VImetal of said first hydrotreating catalyst is selected from Mo, W, andmixtures thereof, and high surface area support material is selectedfrom silica, alumina, and mixtures thereof.
 23. The process according toclaim 18 wherein said bulk metal hydrotreating catalyst comprises oneGroup VIII non-noble metal and two Group VIB metals wherein the molarratio of Group VIB to Group VIII non-noble metals ranges from 10:1-1:10.24. The process according to claim 23 wherein the at least one GroupVIII non-noble metal and at least one Group VIB metals are present asoxidic compounds of the corresponding metals, or if the catalystcomposition has been sulfided, sulfidic compounds of the correspondingmetals.
 25. The process according to claim 18 wherein the bulk metalhydrotreating catalysts have a surface area of at least 50 m²/g, a poresize volume of about 0.05 to about 5 ml/g, and a median diameter of atleast 50 nm.
 26. The process according to claim 18 wherein saideffective hydrotreating conditions include temperatures of from 150 to400° C., a hydrogen partial pressure of from 1480 to 20786 kPa (200 to3000 psig), a space velocity of from 0.1 to 10 liquid hourly spacevelocity (LHSV), and a hydrogen to feed ratio of from 89 to 1780 m³/m³(500 to 10000 scf/B).
 27. The process according to claim 18 wherein thecatalyst system of the present invention comprises about 5-95 vol. % ofthe first hydrotreating catalyst with the second hydrotreating catalystcomprising the remainder.
 28. The process according to claim 18 whereinsaid first hydrotreating catalyst has an average pore diameter ofgreater than 11 nm.
 29. The process according to claim 18 wherein saidfirst hydrotreating catalyst has an average pore diameter of greaterthan 12 nm.
 30. The process according to claim 27 wherein the catalystsystem of the present invention comprises about 40-60 vol. % of thefirst hydrotreating catalyst with the second hydrotreating catalystcomprising the remainder.
 31. The process according to claim 18 whereinthe catalyst system of the present invention comprises about 5-50 vol. %of the first hydrotreating catalyst with the second hydrotreatingcatalyst comprising the remainder.